CN112480387A - High molecular weight macromonomer polyether, polycarboxylate superplasticizer and preparation method thereof - Google Patents
High molecular weight macromonomer polyether, polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The application relates to high molecular weight macromonomer polyether which is characterized by being prepared from the following raw material components: (a) a hydroxy acrylate; (b) an epoxide; and (c) a catalyst; wherein the epoxide is ethylene oxide, propylene oxide or a mixture thereof, and the high molecular weight macromonomer polyether has a weight average molecular weight of 2800-5000. The present application also relates to a process for the preparation of the high molecular weight macromonomer polyethers as described above. The present application also relates to polycarboxylic acid water reducing agents prepared from the high molecular weight macromonomer polyethers described above. The high molecular weight macromonomer polyether prepared in the method has low impurity content, obviously improves the reaction conversion rate, further improves the yield of target products, and has the characteristics of environmental protection, safety and benefit win-win. Finally, the high molecular weight macromonomer polyethers described herein have low viscosity and the polycarboxylic acid water reducing agents prepared therefrom have good workability and flowability.
Description
Technical Field
The application relates to the technical field of organic chemistry and building materials, in particular to high molecular weight macromonomer polyether, a polycarboxylate superplasticizer prepared from the high molecular weight macromonomer polyether and a preparation method of the high molecular weight macromonomer polyether.
Background
The water reducing agent is widely applied to the field of buildings, particularly to the aspect of concrete mortar, and can obviously improve the performance of concrete products, reduce the addition of water and shorten the curing time. In recent years, the method is widely applied to the construction of high-speed railways in China and is also widely used by civil buildings.
The existing production of the monomer polyether of the water reducing agent generally adopts an intermittent kettle type production, and due to the performance influence of the monomer polyether in the production process, the viscosity of the product is higher, the quality is lower, so that the inconvenience is brought to a part of products in the use process, the pollution is caused, and the resources are wasted.
The existing production method has the following disadvantages: (1) the epoxide component is small; (2) the viscosity is higher in use, which causes problems; (3) resources are wasted; (4) the production safety is not high; (5) the molecular weight is low. In addition, the high viscosity of the product and possible side reactions affect the performance of the water reducing agent. At present, along with the improvement of national building energy-saving requirements, the using amount of the polycarboxylate superplasticizer is greatly increased. Along with the gradual increase of the demand and the yield of the monomer polyether of the water reducing agent, the problem of reducing the viscosity in the production process of the monomer polyether of the water reducing agent needs to be solved urgently, the side reaction product influences the quality of the polycarboxylate water reducing agent, the negative influence is brought to the environmental protection, and the using amount of the water reducing agent is reduced.
For this reason, there is a continuing need in the art to develop a high molecular weight macromonomer polyether having a low viscosity and few side reactions, and a method for preparing the same.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, the molecular weight of polyether of a polycarboxylate water reducer monomer is not high, the viscosity reduction effect is poor, the reaction time is long, byproducts are more, the prepared polyether of the polycarboxylate water reducer monomer has more impurities, the viscosity is high, the use is inconvenient and the like, and provides the high-molecular-weight macromonomer polyether for preparing the polycarboxylate water reducer.
It is also an object of the present invention to provide a process for the preparation of the high molecular weight macromonomer polyethers as described above.
It is also an object of the present application to provide a polycarboxylic acid water reducer prepared from a high molecular weight macromonomer polyether as described above.
In order to solve the above technical problems, the present application provides the following technical solutions.
In a first aspect, the present application provides a high molecular weight macromonomer polyether characterized in that the high molecular weight macromonomer polyether is made from the following raw material components:
(a) a hydroxy acrylate;
(b) an epoxide;
and (c) a catalyst;
wherein the epoxide is ethylene oxide, propylene oxide or a mixture thereof;
wherein the weight average molecular weight of the high molecular weight macromonomer polyether is 2800-5000.
In one embodiment, the high molecular weight macromonomer polyether has a weight average molecular weight of 2600, 2800, 3000, 3500, 4000, 4800, 5000, or a range or subrange therebetween any two values thereof.
In one embodiment of the first aspect, the high molecular weight macromonomer polyethers are prepared from the following raw material components in parts by weight:
(a) 100 parts by weight of acrylic acid hydroxy ester;
(b) 1800 parts by weight of epoxide and 2100 parts by weight;
and (c) 0.3 to 2.5 parts by weight of a catalyst.
In one embodiment, the epoxide is present in an amount of 1800 parts by weight, 1900 parts by weight, 2000 parts by weight, 2100 parts by weight, or a range or subrange therebetween, when the hydroxy acrylate is present in an amount of 100 parts by weight.
In one embodiment, the catalyst is used in an amount of 0.3 parts by weight, 0.5 parts by weight, 1.0 parts by weight, 1.5 parts by weight, 2.0 parts by weight, 2.5 parts by weight, or a range or sub-range between any two of these values, when the hydroxy acrylate is used in an amount of 100 parts by weight.
In one embodiment of the first aspect, the hydroxy acrylate is selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate.
In one embodiment of the first aspect, the catalyst is one or more of a hydroxide of an alkali metal, an alcohol salt of an alkali metal, a hydride of an alkali metal, a double metal cyanide complex (DMC).
In a second aspect, the present application provides a process for the preparation of a high molecular weight macromonomer polyether as described in the first aspect, characterized in that the process comprises the steps of:
s1: reacting the hydroxyl acrylate with the catalyst under an inert atmosphere to obtain a high molecular weight macromonomer polyether intermediate;
and, S2: reacting the high molecular weight macromonomer polyether intermediate with the epoxide in an inert atmosphere, and curing to obtain the high molecular weight macromonomer polyether;
wherein, in step S2, the reaction temperature is 95-165 ℃ and the reaction pressure is less than or equal to 0.3 MPa.
In one embodiment of the second aspect, in step S1, the high molecular weight macromonomer polyether intermediate has a weight average molecular weight of 800.
In one embodiment of the second aspect, the reaction temperature is 100 ℃ to 145 ℃ and not more than 155 ℃ at the most in step S2.
In one embodiment of the second aspect, in step S2, the reaction pressure is less than or equal to 0.2 MPa.
In a third aspect, the present application provides a polycarboxylic acid water reducing agent characterized in that it is made from the high molecular weight macromonomer polyether of the first aspect, an unsaturated acid, a chain extender and an auxiliary. In a specific embodiment, the auxiliary agents comprise an oxidizing agent, a reducing agent, water and other auxiliary agents required for preparing the polycarboxylic acid water reducing agent.
In one embodiment of the third aspect, the weight ratio of the high molecular weight macromonomer polyether to the unsaturated acid is 360: 30.
Compared with the prior art, the invention has the advantages that: in the process of preparing the high molecular weight macromonomer polyether, an alcohol initiator and a catalyst are mixed and reacted for stirring, so that the residue of epoxide and side reaction are further reduced, the by-product is reduced to below 2% from 5%, the reaction conversion rate is obviously improved, and the yield of the target product is further improved. In addition, the preparation method of the high molecular weight macromonomer polyether also relieves the discharge pressure of residual epoxide, indirectly increases the profit margin of products, and has the characteristics of environmental protection, safety and benefit win-win. Finally, the high molecular weight macromonomer polyethers described herein have low viscosity and the polycarboxylic acid water reducing agents prepared therefrom have good workability and flowability.
Drawings
FIG. 1 shows the GPC spectrum of the high molecular weight macromonomer polyether according to example 3.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical, or other property (e.g., molecular weight, melt index, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. These are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. It should also be noted that the terms "first," "second," and the like herein do not define a sequential order, but merely distinguish between different structures.
When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
In a first aspect, the application provides a preparation method of novel macromonomer polyether of polycarboxylic acid water reducing agent, which overcomes the defects of low molecular weight and poor viscosity reduction effect of the monomer polyether, can obviously reduce the viscosity of the water reducing agent and reduce the damage of equipment, and has safe production process, simple and convenient operation method, and the novel macromonomer polyether of polycarboxylic acid water reducing agent prepared by the method has less impurities.
In a specific embodiment, the application provides a preparation method of a polycarboxylic acid water reducer viscosity-reducing monomeric polyether, which comprises the following steps: stirring the hydroxyl acrylate initiator uniformly in a reaction kettle with a nitrogen bubbling device, and detecting the moisture; then under the action of proper catalyst, adding ethylene oxide, propylene oxide or their mixture to make its weight-average molecular weight be up to 2400 or above so as to obtain the high-molecular-weight macromonomer polyether. When the water content is detected, the water content is qualified when the water content is less than 0.05%, if the water content is unqualified, the impurity content in the product is high, wherein the impurity is mainly PEG, the synthesis of the water reducing agent is influenced, a large amount of foam is generated in the synthesis, and the water reducing rate and other indexes of the water reducing agent are seriously influenced.
At present, no related product is applied to the synthesis of the water reducing agent mother liquor, and the monomer polyether can play a role in reducing the viscosity of the mother liquor and improving the water reducing performance.
In one embodiment, the hydroxy acrylate initiator may be an acrylate initiator commonly used in the art, and is preferably one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, and hydroxybutyl methacrylate. More preferably hydroxybutyl acrylate and/or hydroxybutyl methacrylate.
The catalyst can be one or more of alkali metal hydroxide, alkali metal alcohol salt and alkali metal hydride and DMC commonly used in the field. The hydride of an alkali metal is preferably potassium hydride. The DMC catalysts described are preferred.
In one embodiment, the mass ratio of the catalyst to the hydroxy acrylate initiator is preferably 0.3-1.5 parts to 100 parts, more preferably 2.1 parts to 100 parts.
In one embodiment, the mass ratio of the DMC catalyst to the hydroxy acrylate starter is preferably 10-30ppm to 1000 parts, more preferably 20ppm to 1000 parts.
In a specific embodiment, the reaction kettle with the ventilating device can be obtained by installing a ventilating device on a reaction kettle commonly used in the field, and the purpose of the ventilating device is to enable an inert gas, such as nitrogen, to be introduced during the reaction process to exhaust oxygen in the reaction kettle, so as to ensure that the reaction is carried out safely. The reaction kettle with the ventilating device preferably comprises an emptying device, a glove box and a vacuum pipeline.
The evacuation device may be one conventionally used in the art, such as a conventional reactor vent line.
In one embodiment, the reaction temperature is preferably 95 to 165 ℃.
In one embodiment, the reaction pressure is preferably 0.3MPa or less.
In the present invention, the term "high molecular weight macromonomer polyether intermediate" generally refers to an alkali metal alkoxide obtained by reacting a hydroxyl group of a hydroxyl acrylate initiator with a catalyst and then substituting the hydrogen of the hydroxyl group of the alcohol initiator with an alkali metal ion contained in the catalyst.
In a preferred embodiment, the invention provides a preparation method of novel macromonomer polyether of polycarboxylic acid water reducing agent, which comprises the following steps:
1) reacting hydroxy acrylate with a catalyst to obtain a high molecular weight macromonomer polyether intermediate;
2) reacting the polycarboxylic acid water reducer intermediate obtained in the step 1) with an epoxide.
In the preparation method of the polycarboxylic acid water reducing agent monomeric polyether, the epoxide can be various epoxides conventionally used in the field, preferably one or more of ethylene oxide and propylene oxide (mainly ethylene oxide and propylene oxide are used). In the preparation method of the polycarboxylate-type water reducer monomeric polyether, the step 2) can be carried out according to the conventional method in the field, and the conventional conditions and steps of the reaction in the field can be referred to for each reaction condition and step. The following conditions are preferred in the present invention: the reaction temperature is preferably 140 ℃ or lower.
The mass percentage of the high molecular weight macromonomer polyether intermediate obtained in the step 1) to the epoxide is preferably 0.2; the progress of the reaction can be monitored by conventional means, typically using changes in reaction pressure and temperature, and is generally completed after the epoxide addition is complete, and the temperature is maintained for the curing reaction (this step is conventional).
In the preparation method of the polycarboxylic acid water reducer monomeric polyether, the step 2) preferably comprises the following steps: 1) the prepared catalyst is metered into a high-pressure reaction kettle or a reaction kettle of an ethoxy device is internally provided with a catalyst for removing gas polymerization-resistant components such as oxygen and the like; 2) introducing an epoxide; and 3) keeping the reaction temperature for curing for 1-2 hours after the epoxide is added, so as to ensure that the epoxide is completely reacted (the step is a conventional operation).
In the step of introducing the epoxide, the reaction temperature is preferably controlled by metering at a temperature of 100 ℃ and 145 ℃ up to 165 ℃. While controlling the reaction pressure not higher than 0.2 MPA. Preferably 100 ℃ and 145 ℃ up to 155 ℃. While controlling the reaction pressure not higher than 0.2 MPA. When the molecular weight reaches 800 after the addition is finished, adding ethylene oxide, and preferably, the temperature of 100 ℃ and 145 ℃ is not more than 155 ℃. While controlling the reaction pressure not higher than 0.2 MPA. Ethylene oxide was added to a mass fraction of 3000.
The novel monomer polyether of the water reducing agent, namely the high molecular weight macromonomer polyether, is a novel substance, and the improvement of the preparation method, particularly the improvement of the intermediate can obviously improve the quality of the product, so that the impurity content of the product is obviously lower than that of the improved product. When the high molecular weight macromonomer polyether is used for preparing the polycarboxylate superplasticizer, the characteristics of the superplasticizer, such as water reducing performance, collapse retention performance, viscosity reduction performance and the like, can be improved.
In one embodiment, the high molecular weight macromonomer polyethers described herein can have the following structural formula:
In the above formula, n represents the number of repeating units derived from ethylene oxide and m represents the number of repeating units derived from propylene oxide, wherein n and m are positive integers greater than 1 and are selected such that the high molecular weight macromonomer polyether has a weight average molecular weight of 2800-5000.
In the present invention, the term "hydroxyl value" refers to the number of milligrams of potassium hydroxide (KOH) corresponding to the hydroxyl groups in 1g of a sample, expressed as mgKOH/g.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The percentage in the invention is the mass percentage of each component in the total amount of the raw materials.
Examples
The technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present application. The reagents and raw materials used are commercially available unless otherwise specified. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
The raw material formula is as follows: 500 parts of hydroxyethyl acrylate and 2.1 parts of potassium hydroxide.
The preparation method comprises the following steps: 500 parts of hydroxyethyl acrylate are introduced into a reaction vessel equipped with an aeration device which also comprises an evacuation and vacuum system. Stirring uniformly, detecting that the water content is qualified, then starting stirring, and adding 2.1 parts of potassium hydroxide to react to prepare the polycarboxylic acid water reducer monomer polyether intermediate 1. And (3) adding the prepared polycarboxylate water reducing agent monomer polyether intermediate 1 into a high-pressure reaction kettle (or a reaction kettle of an ethoxy device) by metering for replacement to remove gas polymerization-inhibiting components such as oxygen and the like, thereby obtaining a high-molecular-weight macromonomer polyether intermediate 2.
650 parts of propylene oxide are introduced, metered in with the reaction temperature as a control parameter, preferably 100 ℃ and 145 ℃ up to 155 ℃. While controlling the reaction pressure not higher than 0.2 MPA. When the molecular weight reached 800 after the addition was complete, 1650 parts of ethylene oxide were added, preferably at a temperature of 100 ℃ and 145 ℃ and not more than 155 ℃. While controlling the reaction pressure not higher than 0.2 MPA. Adding ethylene oxide to 3000 mass portions, curing at the reaction temperature for 1-2 hours after the epoxide is added, and transferring the mixture into a storage tank for later use after neutralization.
The polyether of the water reducing agent prepared in the embodiment has a hydroxyl value of 18.5mgKOH/g, a yield of 99.07%, and a liquid appearance. The high molecular weight macromonomer polyether according to example 1 was subjected to GPC measurement to find that the average molecular weight of the main peak was 3032, the content% (area normalized) of the main peak was 98.9156, the distribution coefficient Mw/Mn of the main peak was 1.04683, and the molecular weight/content% of impurities was 1.0844.
Example 2
The raw material formula is as follows: 500 parts of hydroxypropyl acrylate and 2.1 parts of potassium hydroxide.
The preparation method comprises the following steps: 500 parts of hydroxypropyl acrylate are introduced into a reaction vessel equipped with an aeration device which also includes an evacuation and vacuum system. Stirring uniformly, detecting that the water content is qualified, then starting stirring, and adding 2.1 parts of potassium hydroxide to react to prepare the polycarboxylic acid water reducer monomer polyether intermediate. And (3) adding the prepared polycarboxylate water reducing agent monomer polyether intermediate 1 into a high-pressure reaction kettle (or a reaction kettle of an ethoxy device) by metering for replacement to remove gas polymerization-inhibiting components such as oxygen and the like, thereby obtaining a high-molecular-weight macromonomer polyether intermediate 2.
650 parts of propylene oxide are introduced, metered in with the reaction temperature as a control parameter, preferably 100 ℃ and 145 ℃ up to 155 ℃. While controlling the reaction pressure not higher than 0.2 MPA. When the molecular weight reached 800 after the addition was complete, 1650 parts of ethylene oxide were added, preferably at a temperature of 100 ℃ and 145 ℃ and not more than 155 ℃. While controlling the reaction pressure not higher than 0.2 MPA. Adding ethylene oxide to 3000 mass portions, curing at the reaction temperature for 1-2 hours after the epoxide is added, and transferring the mixture into a storage tank for later use after neutralization.
The water-reducing agent polyether prepared in this example had a hydroxyl value of 18.7mgKOH/g, a yield of 99.07%, and an appearance of liquid. The high molecular weight macromonomer polyether according to example 2 was subjected to GPC measurement to find that the average molecular weight of the main peak was 3000, the content% (area normalized) of the main peak was 98.8836, the distribution coefficient Mw/Mn of the main peak was 1.05089, and the molecular weight/content% of impurities was 1.1164.
Example 3
The raw material formula is as follows: hydroxybutyl acrylate 500 parts, DMC 30 ppm.
The preparation method comprises the following steps: hydroxybutyl acrylate was charged to a reaction vessel equipped with a nitrogen vent, which also included an evacuation and vacuum system. Stirring uniformly, detecting that the water content is less than 0.05 percent, starting stirring, adding DMC for reaction, stirring for 15 minutes, dehydrating in vacuum, and replacing to remove gas polymerization-resistant components such as oxygen and the like to obtain a high molecular weight macromonomer polyether intermediate 3.
650 parts of propylene oxide are introduced, metered in with the reaction temperature as a control parameter, preferably 100 ℃ and 145 ℃ up to 155 ℃. While controlling the reaction pressure not higher than 0.2 MPA. When the molecular weight reaches 800, the propylene oxide feed is stopped and the ethylene oxide feed is started 1650 parts, preferably 100 ℃ 145 ℃ up to 155 ℃. Meanwhile, the reaction pressure is controlled to be not higher than 0.2MPA, when the molecular weight reaches 3000, the reaction temperature is kept for curing for 0.5 to 1 hour, and the materials are prepared for standby discharge.
The polyether hydroxyl value of the water reducing agent prepared by the embodiment is 18.9mgKOH/g, the yield is 99.2%, and the appearance is liquid. The impurity level was measured at 1.08% (chromatography). The high molecular weight macromonomer polyether according to example 3 has an average molecular weight of 2599 as measured by GPC, a main peak content (area normalized) of 98.9156%, a main peak distribution coefficient Mw/Mn of 1.04683, and a% impurity molecular weight/content of 6457/1.0844.
Example of mother liquor for synthesizing water reducing agent:
example 4
360 g of hydroxyethyl acrylate polyoxyethylene ether (Mw is 3000) prepared according to example 1 is added into a clean four-neck flask, then 300 g of deionized water is added, the mixture is stirred at normal temperature for 30 minutes to fully dissolve the monomers, and material A is dropwise added to prepare 30 g of acrylic acid, 1.6 g of mercaptopropionic acid and 70 g of deionized water, and the mixture is uniformly stirred for later use. 0.8 g of vitamin C and 50 g of deionized water are prepared by dropwise adding the material B, and the mixture is uniformly stirred for later use. After the dropwise addition material preparation is finished, 3.5 g of 30% hydrogen peroxide by mass is added into the flask, after stirring for 3 minutes, the material A and the material B begin to be dropwise added simultaneously, wherein the material A is dropwise added for 40 minutes, the material B is dropwise added for 50 minutes, after the dropwise addition is finished, the temperature is kept for 1 hour, and then 165.1 g of water is supplemented to obtain 40% mother liquor. The reaction temperature is controlled between 19 ℃ and 21 ℃ in the whole reaction process.
Example 5
360 g of hydroxypropyl acrylate polyoxyethylene ether (Mw is 3000) prepared according to example 2 is added into a clean four-neck flask, then 300 g of deionized water is added, the mixture is stirred for 30 minutes at normal temperature to fully dissolve the monomers, and the material A is dropwise added to prepare 30 g of acrylic acid, 1.6 g of mercaptopropionic acid and 70 g of deionized water, and the mixture is uniformly stirred for standby. 0.8 g of vitamin C and 50 g of deionized water are prepared by dropwise adding the material B, and the mixture is uniformly stirred for later use. After the dropwise addition material preparation is finished, 3.5 g of 30% hydrogen peroxide by mass is added into the flask, after stirring for 3 minutes, the material A and the material B begin to be dropwise added simultaneously, wherein the material A is dropwise added for 40 minutes, the material B is dropwise added for 50 minutes, after the dropwise addition is finished, the temperature is kept for 1 hour, and then 165.1 g of water is supplemented to obtain 40% mother liquor. The reaction temperature is controlled between 19 ℃ and 21 ℃ in the whole reaction process.
Example 6
360 g of hydroxybutyl acrylate polyoxyethylene ether (Mw is 3000) prepared according to example 3 is added into a clean four-neck flask, then 300 g of deionized water is added, the mixture is stirred for 30 minutes at normal temperature to fully dissolve the monomers, and the material A is dropwise added to prepare 30 g of acrylic acid, 1.6 g of mercaptopropionic acid and 70 g of deionized water, and the mixture is uniformly stirred for standby. 0.8 g of vitamin C and 50 g of deionized water are prepared by dropwise adding the material B, and the mixture is uniformly stirred for later use. After the dropwise addition material preparation is finished, 3.5 g of 30% hydrogen peroxide by mass is added into the flask, after stirring for 3 minutes, the material A and the material B begin to be dropwise added simultaneously, wherein the material A is dropwise added for 40 minutes, the material B is dropwise added for 50 minutes, after the dropwise addition is finished, the temperature is kept for 1 hour, and then 165.1 g of water is supplemented to obtain 40% mother liquor. The reaction temperature is controlled between 19 ℃ and 21 ℃ in the whole reaction process.
Comparative example 1
Adding 360 g of isopentenol polyoxyethylene ether (Mw is 2400), then adding 300 g of deionized water, stirring at normal temperature for 30 minutes to fully dissolve the monomers, dropwise adding the material A to prepare 50 g of acrylic acid, 1.6 g of mercaptopropionic acid and 70 g of deionized water, and stirring uniformly for later use. 0.8 g of vitamin C and 50 g of deionized water are prepared by dropwise adding the material B, and the mixture is uniformly stirred for later use. After the dropwise addition material preparation is finished, 3.5 g of 30% hydrogen peroxide by mass is added into the flask, after stirring for 3 minutes, dropwise addition of the material A and the material B is started simultaneously, wherein the material A is dropwise added for 180 minutes, the material B is dropwise added for 210 minutes, after the dropwise addition is finished, heat is preserved for 1 hour, and then 165.1 g of water is supplemented to obtain 40% mother liquor. The reaction temperature is controlled between 19 ℃ and 21 ℃ in the whole reaction process.
The polycarboxylic acid water reducing agents of examples 4 to 6 and comparative example 1 were subjected to performance test and comparison in accordance with GB/T50080-2016.
The results of the performance test of the polycarboxylic acid water reducing agents according to examples 4 to 6 and comparative example 1 are shown in Table 1 below.
TABLE 1 polycarboxylic acid water reducing agent concrete test results of examples 3-5 and comparative example 1
As can be seen from Table 1, the macromonomer polyether synthesized by using acrylates as an initiator is applied to concrete after synthesis of a mother liquor, and the data of the product is obviously better than that of the comparative example, which is obviously shown that the spreading degree and the slump at 2 hours are respectively 580/560/545 and are obviously higher than that of the comparative example 540. The concrete was better in state than the comparative example, and better than the comparative example 1 in workability, the examples showed excellent workability without changing the compounding ratio in the comparative example 1, and further, 3 examples were better than the comparative example in concrete flow. It should be noted that, the comparison is performed under the condition that the proportioning of the water reducing agent mother liquor is basically unchanged, if the comparison is improved, macromolecular acid needs to be further added into the comparison example, the increased cost is not favorable for reaction control in the synthesis, and certain adverse effect can be caused to the application.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (10)
1. A high molecular weight macromonomer polyether is characterized in that the high molecular weight macromonomer polyether is prepared from the following raw material components:
(a) a hydroxy acrylate;
(b) an epoxide;
and (c) a catalyst;
wherein the epoxide is ethylene oxide, propylene oxide or a mixture thereof;
wherein the weight average molecular weight of the high molecular weight macromonomer polyether is 2800-5000.
2. A high molecular weight macromonomer polyether as claimed in claim 1 wherein said high molecular weight macromonomer polyether is prepared from the following raw materials in parts by weight:
(a) 100 parts by weight of acrylic acid hydroxy ester;
(b) 1800 parts by weight of epoxide and 2100 parts by weight;
and (c) 0.3 to 1.5 parts by weight of a catalyst.
3. A high molecular weight macromonomer polyether as claimed in claim 1 or 2 wherein said hydroxy acrylate is selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate and hydroxybutyl methacrylate.
4. A high molecular weight macromonomer polyether as claimed in claim 1 or 2 wherein said catalyst is one or more of alkali metal hydroxide, alkali metal alcohol salt, alkali metal hydride, double metal cyanide complex DMC.
5. A process for the preparation of a high molecular weight macromonomer polyether as claimed in any one of claims 1 to 4 comprising the steps of:
s1: reacting the hydroxyl acrylate with the catalyst under an inert atmosphere to obtain a high molecular weight macromonomer polyether intermediate;
and, S2: reacting the high molecular weight macromonomer polyether intermediate with the epoxide in an inert atmosphere, and curing to obtain the high molecular weight macromonomer polyether;
wherein, in step S2, the reaction temperature is 95-165 ℃ and the reaction pressure is less than or equal to 0.3 MPa.
6. The method of claim 5 wherein in step S1, the high molecular weight macromonomer polyether intermediate has a weight average molecular weight of 800.
7. The method as claimed in claim 5, wherein the reaction temperature in step S2 is 100 ℃ and 145 ℃ and not more than 155 ℃.
8. The method according to claim 5, wherein in step S2, the reaction pressure is 0.2MPa or less.
9. A polycarboxylic acid water reducing agent characterized in that it is made from the high molecular weight macromonomer polyether of any one of claims 1 to 4, an unsaturated acid, a chain extender and an auxiliary agent.
10. The polycarboxylate water reducer of claim 9, characterized in that the weight ratio of said high molecular weight macromonomer polyether to said unsaturated acid is 360: 30.
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| CN106317402A (en) * | 2016-08-19 | 2017-01-11 | 浙江皇马科技股份有限公司 | Polyether monomer and preparation method and application thereof |
| CN109679084A (en) * | 2018-12-10 | 2019-04-26 | 上海东大化学有限公司 | A kind of high molecular weight viscosity reduction type polyethers and preparation method thereof |
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| CN102993432A (en) * | 2012-10-19 | 2013-03-27 | 江苏博特新材料有限公司 | Water reducer midbody, preparation method thereof and water reducer prepared by using preparation method |
| CN106317402A (en) * | 2016-08-19 | 2017-01-11 | 浙江皇马科技股份有限公司 | Polyether monomer and preparation method and application thereof |
| CN109679084A (en) * | 2018-12-10 | 2019-04-26 | 上海东大化学有限公司 | A kind of high molecular weight viscosity reduction type polyethers and preparation method thereof |
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